Dirac Semimetal Heterostructures: 3D Cd3As2 on 2D Graphene

Dirac semimetal is an emerging class of quantum matters, ranging from 2D category, such as, graphene and surface states of topological insulator to 3D category, for instance, Cd₃As₂ and Na₃Bi. As 3D Dirac semimetals typically possess Fermi‐arc surface states, the 2D–3D Dirac van der Waals heterostructures should be promising for future electronics. Here, graphene–Cd₃As₂ heterostructures are fabricated through direct layer‐by‐layer stacking. The electronic coupling results in a notable interlayer charge transfer, which enables us to modulate the Fermi level of graphene through Cd₃As₂. A planar graphene p–n–p junction is achieved by selective modification, which demonstrates quantized conductance plateaus. Moreover, compared with the bare graphene device, the graphene–Cd₃As₂ hybrid device presents large nonlocal signals near the Dirac point due to the charge transfer from the spin‐polarized surface states in the adjacent Cd₃As₂. The results enrich the family of van der Waals heterostructure and should inspire more studies on the application of Dirac/Weyl semimetals in spintronics.     

Site‐Selective and van der Waals Epitaxial Growth of Rhenium Disulfide on Graphene

The surface property of growth substrate imposes significant influence in the growth behaviors of 2D materials. Rhenium disulfide (ReS₂) is a new family of 2D transition metal dichalcogenides with unique distorted 1T crystal structure and thickness‐independent direct bandgap. The role of growth substrate is more critical for ReS₂ owing to its weak interlayer coupling property, which leads to preferred growth along the out‐of‐plane direction while suppressing the uniform in‐plane growth. Herein, graphene is introduced as the growth substrate for ReS₂ and the synthesis of graphene/ReS₂ vertical heterostructure is demonstrated via chemical vapor deposition. Compared with the rough surface of SiO₂/Si substrate with dangling bonds which hinders the uniform growth of ReS₂, the inert and smooth surface nature of graphene sheet provides a lower energy barrier for migration of the adatoms, thereby promoting the growth of ReS₂ on the graphene surface along the in‐plane direction. Furthermore, patterning of the graphene/ReS₂ heterostructure is achieved by the selective growth of ReS₂, which is attributed to the strong binding energy between sulfur atoms and graphene surface. The fundamental studies in the role of graphene as the growth template in the formation of van der Waals heterostructures provide better insights into the synthesis of 2D heterostructures.     

Self‐Assembly of Transition Metal Oxide Nanostructures on MXene Nanosheets for Fast and Stable Lithium Storage

Recently, a new class of 2D materials, i.e., transition metal carbides, nitrides, and carbonitrides known as MXenes, is unveiled with more than 20 types reported one after another. Since they are flexible and conductive, MXenes are expected to compete with graphene and other 2D materials in many applications. Here, a general route is reported to simple self‐assembly of transition metal oxide (TMO) nanostructures, including TiO₂ nanorods and SnO₂ nanowires, on MXene (Ti₃C₂) nanosheets through van der Waals interactions. The MXene nanosheets, acting as the underlying substrate, not only enable reversible electron and ion transport at the interface but also prevent the TMO nanostructures from aggregation during lithiation/delithiation. The TMO nanostructures, in turn, serve as the spacer to prevent the MXene nanosheets from restacking, thus preserving the active areas from being lost. More importantly, they can contribute extraordinary electrochemical properties, offering short lithium diffusion pathways and additional active sites. The resulting TiO₂/MXene and SnO₂/MXene heterostructures exhibit superior high‐rate performance, making them promising high‐power and high‐energy anode materials for lithium‐ion batteries.     

Mesoporous Hollow Sb/ZnS@C Core–Shell Heterostructures as Anodes for High‐Performance Sodium‐Ion Batteries

Combining the advantage of metal, metal sulfide, and carbon, mesoporous hollow core–shell Sb/ZnS@C hybrid heterostructures composed of Sb/ZnS inner core and carbon outer shell are rationally designed based on a robust template of ZnS nanosphere, as anodes for high‐performance sodium‐ion batteries (SIBs). A partial cation exchange reaction based on the solubility difference between Sb₂S₃ and ZnS can transform mesoporous ZnS to Sb₂S₃/ZnS heterostructure. To get a stable structure, a thin contiguous resorcinol‐formaldehyde (RF) layer is introduced on the surface of Sb₂S₃/ZnS heterostructure. The effectively protective carbon layer from RF can be designed as the reducing agent to convert Sb₂S₃ to metallic Sb to obtain core–shell Sb/ZnS@C hybrid heterostructures. Simultaneously, the carbon outer shell is beneficial to the charge transfer kinetics, and can maintain the structure stability during the repeated sodiation/desodiation process. Owing to its unique stable architecture and synergistic effects between the components, the core–shell porous Sb/ZnS@C hybrid heterostructure SIB anode shows a high reversible capacity, good rate capability, and excellent cycling stability by turning the optimized voltage range. This novel strategy to prepare carbon‐layer‐protected metal/metal sulfide core–shell heterostructure can be further extended to design other novel nanostructured systems for high‐performance energy storage devices.     

Heterostructure of 1D Ta3N5 Nanorod/BaTaO2N Nanoparticle Fabricated by a One‐Step Ammonia Thermal Route for Remarkably Promoted Solar Hydrogen Production

Heterostructures are widely fabricated for promotion of photogenerated charge separation and solar cell/fuel production. (Oxy)nitrides are extremely promising for solar energy conversion, but the fabrication of heterostructures based on nitrogen‐containing semiconductors is still challenging. Here, a simple ammonia thermal synthesis of a heterostructure (denoted as Ta₃N₅/BTON) composed of 1D Ta₃N₅ nanorods and BaTaO₂N (BTON) nanoparticles (0D), which is demonstrated to result in a remarkable increase in photogenerated charge separation and solar hydrogen production from water, is introduced. As analyzed and discussed, the Ta₃N₅/BTON heterostructure is type II and tends to create intimate interfaces between the 1D nanorods and 0D nanoparticles. The 1D Ta₃N₅ nanorods are demonstrated to transfer electrons along the rod orientation direction. Furthermore, the intimate interfaces of the heterostructure are believed to originate from the similar Ta‐based octahedron units of Ta₃N₅ and BTON. All of the above features are expected to integrally endow increased photoinduced charge separation and one order of magnitude higher solar overall water splitting activity with respect to counterpart systems. These results may open a new avenue to fabricate heterostructures on the basis of nitrogen‐containing semiconductors that is extremely promising for solar energy conversion.     

Novel Multifunctional Properties Induced by Interface Effects in Perovskite Oxide Heterostructures

Multilayer structures have emerged as a leading research topic and researchers expect that multilayers may lead to interesting artificial materials with novel properties. In this Research News we show that the introduction of interfaces into perovskite oxides can induce a series of novel properties including an unusual positive magnetoresistance, great enhancement of lateral photovoltage in La_0.9Sr_0.1MnO₃/SrNb_0.01Ti_0.99O₃, and an electrical modulation of the magnetoresistance in multi‐p‐n heterostructures of SrTiO_3?δ/La_0.9Sr_0.1MnO₃/SrTiO_3?δ/La_0.9Sr_0.1MnO₃/Si. This novel positive magnetoresistance is attributed to the creation of a space charge region at the interface where the spin of the carriers is anti‐parallel to that of the carriers in the region far from the interface of manganese oxide in the heterostructures.     

High‐Responsivity Graphene/InAs Nanowire Heterojunction Near‐Infrared Photodetectors with Distinct Photocurrent On/Off Ratios

Graphene is a promising candidate material for high‐speed and ultra‐broadband photodetectors. However, graphene‐based photodetectors suffer from low photoreponsivity and I_light/I_dark ratios due to their negligible‐gap nature and small optical absorption. Here, a new type of graphene/InAs nanowire (NW) vertically stacked heterojunction infrared photodetector is reported, with a large photoresponsivity of 0.5 AW^?1 and I_light/I_dark ratio of 5 × 10², while the photoresponsivity and I_light/I_dark ratio of graphene infrared photodetectors are 0.1 mAW^?1 and 1, respectively. The Fermi level (E_F ) of graphene can be widely tuned by the gate voltage owing to its 2D nature. As a result, the back‐gated bias can modulate the Schottky barrier (SB) height at the interface between graphene and InAs NWs. Simulations further demonstrate the rectification behavior of graphene/InAs NW heterojunctions and the tunable SB controls charge transport across the vertically stacked heterostructure. The results address key challenges for graphene‐based infrared detectors, and are promising for the development of graphene electronic and optoelectronic applications.     

Transition Metal Oxides for Organic Electronics: Energetics,Device Physics and Applications

During the last few years, transition metal oxides (TMO) such as molybdenum tri‐oxide (MoO₃), vanadium pent‐oxide (V₂O₅) or tungsten tri‐oxide (WO₃) have been extensively studied because of their exceptional electronic properties for charge injection and extraction in organic electronic devices. These unique properties have led to the performance enhancement of several types of devices and to a variety of novel applications. TMOs have been used to realize efficient and long‐term stable p‐type doping of wide band gap organic materials, charge‐generation junctions for stacked organic light emitting diodes (OLED), sputtering buffer layers for semi‐transparent devices, and organic photovoltaic (OPV) cells with improved charge extraction, enhanced power conversion efficiency and substantially improved long term stability. Energetics in general play a key role in advancing device structure and performance in organic electronics; however, the literature provides a very inconsistent picture of the electronic structure of TMOs and the resulting interpretation of their role as functional constituents in organic electronics. With this review we intend to clarify some of the existing misconceptions. An overview of TMO‐based device architectures ranging from transparent OLEDs to tandem OPV cells is also given. Various TMO film deposition methods are reviewed, addressing vacuum evaporation and recent approaches for solution‐based processing. The specific properties of the resulting materials and their role as functional layers in organic devices are discussed.     

Reconfiguration of Amorphous Complex Oxides: A Route to a Broad Range of Assembly Phenomena,Hybrid Materials,and Novel Functionalities

Reconfiguration of amorphous complex oxides provides a readily controllable source of stress that can be leveraged in nanoscale assembly to access a broad range of 3D geometries and hybrid materials. An amorphous SrTiO₃ layer on a Si:B/Si_1?xGe_x:B heterostructure is reconfigured at the atomic scale upon heating, exhibiting a change in volume of ≈2% and accompanying biaxial stress. The Si:B/Si_1?xGe_x:B bilayer is fabricated by molecular beam epitaxy, followed by sputter deposition of SrTiO₃ at room temperature. The processes yield a hybrid oxide/semiconductor nanomembrane. Upon release from the substrate, the nanomembrane rolls up and has a curvature determined by the stress in the epitaxially grown Si:B/Si_1?xGe_x:B heterostructure. Heating to 600 °C leads to a decrease of the radius of curvature consistent with the development of a large compressive biaxial stress during the reconfiguration of SrTiO₃. The control of stresses via post-deposition processing provides a new route to the assembly of complex-oxide-based heterostructures in 3D geometry. The reconfiguration of metastable mechanical stressors enables i) synthesis of various types of strained superlattice structures that cannot be fabricated by direct growth and ii) technologies based on strain engineering of complex oxides via highly scalable lithographic processes and on large-area semiconductor substrates.     

Simultaneous Enhancement of Charge Separation and Hole Transportation in a TiO2–SrTiO3 Core–Shell Nanowire Photoelectrochemical System

Efficient charge separation and transportation are key factors that determine the photoelectrochemical (PEC) water‐splitting efficiency. Here, a simultaneous enhancement of charge separation and hole transportation on the basis of ferroelectric polarization in TiO₂–SrTiO₃ core–shell nanowires (NWs) is reported. The SrTiO₃ shell with controllable thicknesses generates a considerable spontaneous polarization, which effectively tunes the electrical band bending of TiO₂. Combined with its intrinsically high charge mobility, the ferroelectric SrTiO₃ thin shell significantly improves the charge‐separation efficiency (η_separation) with minimized influence on the hole‐migration property of TiO₂ photoelectrodes, leading to a drastically increased photocurrent density ( J _ph). Specifically, the 10 nm‐thick SrTiO₃ shell yields the highest J _ph and η_separation of 1.43 mA cm^?2 and 87.7% at 1.23 V versus reversible hydrogen electrode, respectively, corresponding to 83% and 79% improvements compared with those of pristine TiO₂ NWs. The PEC performance can be further manipulated by thermal treatment, and the control of SrTiO₃ film thicknesses and electric poling directions. This work suggests a material with combined ferroelectric and semiconducting features could be a promising solution for advancing PEC systems by concurrently promoting the charge‐separation and hole‐transportation properties.     

Controllable Magnetic Proximity Effect and Charge Transfer in 2D Semiconductor and Double-Layered Perovskite Manganese Oxide van der Waals Heterostructure

Optically generated excitonic states (excitons and trions) in transition metal dichalcogenides are highly sensitive to the electronic and magnetic properties of the materials underneath. Modulation and control of the excitonic states in a novel van der Waals (vdW) heterostructure of monolayer MoSe₂ on double-layered perovskite Mn oxide ((La_0.8Nd_0.2)_1.2Sr_1.8Mn₂O₇) is demonstrated, wherein the Mn oxide transforms from a paramagnetic insulator to a ferromagnetic metal. A discontinuous change in the exciton photoluminescence intensity via dielectric screening is observed. Further, a relatively high trion intensity is discovered due to the charge transfer from metallic Mn oxide under the Curie temperature. Moreover, the vdW heterostructures with an ultrathin h-BN spacer layer demonstrate enhanced valley splitting and polarization of excitonic states due to the proximity effect of the ferromagnetic spins of Mn oxide. The controllable h-BN thickness in vdW heterostructures reveals a several-nanometer-long scale of charge transfer as well as a magnetic proximity effect. The vdW heterostructure allows modulation and control of the excitonic states via dielectric screening, charge carriers, and magnetic spins.     

High Detectivity and Transparent Few‐Layer MoS2/Glassy‐Graphene Heterostructure Photodetectors

Layered van der Waals heterostructures have attracted considerable attention recently, due to their unique properties both inherited from individual two‐dimensional (2D) components and imparted from their interactions. Here, a novel few‐layer MoS₂/glassy‐graphene heterostructure, synthesized by a layer‐by‐layer transfer technique, and its application as transparent photodetectors are reported for the first time. Instead of a traditional Schottky junction, coherent ohmic contact is formed at the interface between the MoS₂ and the glassy‐graphene nanosheets. The device exhibits pronounced wavelength selectivity as illuminated by monochromatic lights. A responsivity of 12.3 mA W^?1 and detectivity of 1.8 × 10¹⁰ Jones are obtained from the photodetector under 532 nm light illumination. Density functional theory calculations reveal the impact of specific carbon atomic arrangement in the glassy‐graphene on the electronic band structure. It is demonstrated that the band alignment of the layered heterostructures can be manipulated by lattice engineering of 2D nanosheets to enhance optoelectronic performance.     

3D Mesoporous van der Waals Heterostructures for Trifunctional Energy Electrocatalysis

The emergence of van der Waals (vdW) heterostructures of 2D materials has opened new avenues for fundamental scientific research and technological applications. However, the current concepts and strategies of material engineering lack feasibilities to comprehensively regulate the as‐obtained extrinsic physicochemical characters together with intrinsic properties and activities for optimal performances. A 3D mesoporous vdW heterostructure of graphene and nitrogen‐doped MoS₂ via a two‐step sequential chemical vapor deposition method is constructed. Such strategy is demonstrated to offer an all‐round engineering of 2D materials including the morphology, edge, defect, interface, and electronic structure, thereby leading to robustly modified properties and greatly enhanced electrochemical activities. The hydrogen evolution is substantially accelerated on MoS₂, while the oxygen reduction and evolution are significantly improved on graphene. This work provides a powerful overall engineering strategy of 2D materials for electrocatalysis, which is also enlightening for other nanomaterials and energy‐related applications.     

Efficient All-Optical Plasmonic Modulators with Atomically Thin Van Der Waals Heterostructures

All-optical modulators are attracting significant attention due to their intrinsic perspective on high-speed, low-loss, and broadband performance, which are promising to replace their electrical counterparts for future information communication technology. However, high-power consumption and large footprint remain obstacles for the prevailing nonlinear optical methods due to the weak photon–photon interaction. Here, efficient all-optical mid-infrared plasmonic waveguide and free-space modulators in atomically thin graphene-MoS₂ heterostructures based on the ultrafast and efficient doping of graphene with the photogenerated carrier in the monolayer MoS₂ are reported. Plasmonic modulation of 44 cm⁻¹ is demonstrated by an LED with light intensity down to 0.15 mW cm⁻², which is four orders of magnitude smaller than the prevailing graphene nonlinear all-optical modulators (≈10³ mW cm⁻²). The ultrafast carrier transfer and recombination time of photogenerated carriers in the heterostructure may achieve ultrafast modulation of the graphene plasmon. The demonstration of the efficient all-optical mid-infrared plasmonic modulators, with chip-scale integrability and deep-sub wavelength light field confinement derived from the van der Waals heterostructures, may be an important step toward on-chip all-optical devices.     

Extreme Reconfigurable Nanoelectronics at the CaZrO3/SrTiO3 Interface

Complex oxide heterostructures have fascinating emergent properties that originate from the properties of the bulk constituents as well as from dimensional confinement. The conductive behavior of the polar/nonpolar LaAlO₃/SrTiO₃ interface can be reversibly switched using conductive atomic force microscopy (c‐AFM) lithography, enabling a wide range of devices and physics to be explored. Here, extreme nanoscale control over the CaZrO₃/SrTiO₃ (CZO/STO) interface, which is formed from two materials that are both nonpolar, is reported. Nanowires with measured widths as narrow as 1.2 nm are realized at the CZO/STO interface at room temperature by c‐AFM lithography. These ultrathin nanostructures have spatial dimensions at room temperature that are comparable to single‐walled carbon nanotubes, and hold great promise for alternative oxide‐based nanoelectronics, as well as offer new opportunities to investigate the electronic structure of the complex oxide interfaces. The cryogenic properties of devices constructed from quasi‐1D channels, tunnel barriers, and planar gates exhibit gate‐tunable superconductivity, quantum oscillations, electron pairing outside of the superconducting regime, and quasi‐ballistic transport. This newly demonstrated ability to control the metal–insulator transition at nonpolar oxide interface greatly expands the class of materials whose behavior can be patterned and reconfigured at extreme nanoscale dimensions.     

Structural defects and local chemistry across ferroelectric–electrode interfaces in epitaxial heterostructures

We present a detailed investigation of the chemistry at the growth interface between the bottom electrode and ferroelectric film in (001)-oriented epitaxial ferroelectric thin-film heterostructures. Three different ferroelectric systems, namely PbZr_0.2Ti_0.8O₃, PbZr_0.52Ti_0.48O₃, and BaTiO₃ deposited on SrRuO₃/SrTiO₃, were investigated to compare and contrast the role of lattice mismatch versus the volatility of the deposited cation species. A combination of transmission electron microscopy-based imaging and spectroscopy reveals distinct correlations among the ferroelectric thin-film composition, the deposition process, and chemical gradients observed across the ferroelectric–electrode interface. Sr diffusion from the electrode into the ferroelectric film was found to be dominant in PbZr_0.2Ti_0.8O₃/SrRuO₃/SrTiO₃ thin films. Conversely, Pb diffusion was found to be prevalent in PbZr_0.52Ti_0.48O₃/SrRuO₃/SrTiO₃ thin films. The BaTiO₃/SrRuO₃/SrTiO₃ heterostructure was found to have atomically sharp interfaces with no signature of any interdiffusion. We show that controlling the volatility of the cation species is as crucial as lattice mismatch in the fabrication of defect-free ferroelectric thin-film devices.     

A General and Straightforward Route to Noble Metal‐Decorated Mesoporous Transition‐Metal Oxides with Enhanced Gas Sensing Performance

Controllable and efficient synthesis of noble metal/transition‐metal oxide (TMO) composites with tailored nanostructures and precise components is essential for their application. Herein, a general mercaptosilane‐assisted one‐pot coassembly approach is developed to synthesize ordered mesoporous TMOs with agglomerated‐free noble metal nanoparticles, including Au/WO₃, Au/TiO₂, Au/NbO_x, and Pt/WO₃. 3‐mercaptopropyl trimethoxysilane is applied as a bridge agent to cohydrolyze with metal oxide precursors by alkoxysilane moieties and interact with the noble metal source (e.g., HAuCl₄ and H₂PtCl₄) by mercapto (? SH) groups, resulting in coassembly with poly(ethylene oxide)‐b‐polystyrene. The noble metal decorated TMO materials exhibit highly ordered mesoporous structure, large pore size (≈14–20 nm), high specific surface area (61–138 m² g^?1), and highly dispersed noble metal (e.g., Au and Pt) nanoparticles. In the system of Au/WO₃, in situ generated SiO₂ incorporation not only enhances their thermal stability but also induces the formation of ε‐phase WO₃ promoting gas sensing performance. Owning to its specific compositions and structure, the gas sensor based on Au/WO₃ materials possess enhanced ethanol sensing performance with a good response (R_air/R_gas = 36–50 ppm of ethanol), high selectivity, and excellent low‐concentration detection capability (down to 50 ppb) at low working temperature (200 °C).     

Electro-Optic Upconversion in van der Waals Heterostructures via Nonequilibrium Photocarrier Tunneling

Ultrafast interlayer charge transfer is one of the most distinct features of van der Waals (vdW) heterostructures. Its dynamics competes with carrier thermalization such that the energy of nonthermalized photocarriers may be harnessed by band engineering. In this study, nonthermalized photocarrier energy is harnessed to achieve near-infrared (NIR) to visible light upconversion in a metal–insulator–semiconductor (MIS) vdW heterostructure tunnel diode consisting of few-layer graphene (FLG), hexagonal boron nitride (hBN), and monolayer tungsten disulfide (WS₂). Photoexcitation of the electrically biased heterostructure with 1.58 eV NIR laser in the linear absorption regime generates emission from the ground exciton state of WS₂, which corresponds to upconversion by ≈370 meV. The upconversion is realized by electrically assisted interlayer transfer of nonthermalized photoexcited holes from FLG to WS₂, followed by formation and radiative recombination of excitons in WS₂. The photocarrier transfer rate can be described by Fowler–Nordheim tunneling mechanism and is electrically tunable by two orders of magnitude by tuning voltage bias applied to the device. This study highlights the prospects for realizing novel electro-optic upconversion devices by exploiting electrically tunable nonthermalized photocarrier relaxation dynamics in vdW heterostructures.     

Multi‐Nonvolatile State Resistive Switching Arising from Ferroelectricity and Oxygen Vacancy Migration

Resistive switching phenomena form the basis of competing memory technologies. Among them, resistive switching, originating from oxygen vacancy migration (OVM), and ferroelectric switching offer two promising approaches. OVM in oxide films/heterostructures can exhibit high/low resistive state via conducting filament forming/deforming, while the resistive switching of ferroelectric tunnel junctions (FTJs) arises from barrier height or width variation while ferroelectric polarization reverses between asymmetric electrodes. Here the authors demonstrate a coexistence of OVM and ferroelectric induced resistive switching in a BaTiO₃ FTJ by comparing BaTiO₃ with SrTiO₃ based tunnel junctions. This coexistence results in two distinguishable loops with multi‐nonvolatile resistive states. The primary loop originates from the ferroelectric switching. The second loop emerges at a voltage close to the SrTiO₃ switching voltage, showing OVM being its origin. BaTiO₃ based devices with controlled oxygen vacancies enable us to combine the benefits of both OVM and ferroelectric tunneling to produce multistate nonvolatile memory devices.     

Enhanced Photocatalytic Property of Reduced Graphene Oxide/TiO2 Nanobelt Surface Heterostructures Constructed by an In Situ Photochemical Reduction Method

A facile method is proposed to assemble graphene oxide (GO) on the surface of a TiO₂ nanobelt followed by an in situ photocatalytic reduction to form reduced graphene oxide (rGO)/TiO₂ nanobelt surface heterostructures. The special colloidal properties of GO and TiO₂ nanobelt are exploited as well as the photocatalytic properties of TiO₂. Using water–ethanol solvent mixtures, GO nanosheets are tightly wrapped around the surface of the TiO₂ nanobelts through an aggregation process and are then reduced in situ under UV‐light irradiation to form rGO/TiO₂ nanobelt surface heterostructures. The heterostructures enhance the separation of the photoinduced carriers, which results in a higher photocurrent due to the special electronic characteristics of rGO. Compared to TiO₂ nanobelts, the rGO/TiO₂ nanobelt surface heterostructures possess higher photocatalytic activity for the degradation of methyl orange and for the production of hydrogen from water, as well as excellent recyclability, with no loss of activity over five cycles.